ES2637548T3 - Procedure for the preparation of polymers as well as reactor for the realization of the procedure - Google Patents
Procedure for the preparation of polymers as well as reactor for the realization of the procedure Download PDFInfo
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- ES2637548T3 ES2637548T3 ES10701553.9T ES10701553T ES2637548T3 ES 2637548 T3 ES2637548 T3 ES 2637548T3 ES 10701553 T ES10701553 T ES 10701553T ES 2637548 T3 ES2637548 T3 ES 2637548T3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/14—Organic medium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
Abstract
Procedimiento para la preparación de polímeros a partir de monómeros y/u oligómeros, en el que un líquido que contiene los monómeros y/u oligómeros se introduce gota a gota en una fase líquida continua en un reactor, en el que la fase líquida continua no es miscible con el líquido que contiene los monómeros y/u oligómeros, y los monómeros y/u oligómeros reaccionan en la fase líquida continua para dar el polímero, en el que el líquido que contiene los monómeros y/u oligómeros se conforma fuera de la fase líquida continua para dar gotas, que se introducen a continuación en la fase líquida continua, caracterizado por que el reactor está configurado como reactor tubular.Process for the preparation of polymers from monomers and / or oligomers, in which a liquid containing the monomers and / or oligomers is introduced dropwise into a continuous liquid phase in a reactor, in which the continuous liquid phase does not it is miscible with the liquid containing the monomers and / or oligomers, and the monomers and / or oligomers react in the continuous liquid phase to give the polymer, in which the liquid containing the monomers and / or oligomers is formed outside the Continuous liquid phase to give drops, which are then introduced into the continuous liquid phase, characterized in that the reactor is configured as a tubular reactor.
Description
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DESCRIPCIONDESCRIPTION
Procedimiento para la preparacion de pollmeros as! como reactor para la realizacion del procedimientoProcedure for the preparation of polymers as! as a reactor for carrying out the procedure
La invencion se refiere a un procedimiento para la preparacion de pollmeros a partir de monomeros y/u oligomeros, en el que un llquido que contiene los monomeros y/u oligomeros se introduce gota a gota en una fase llquida continua en un reactor, en el que la fase llquida continua no es miscible con el llquido que contiene los monomeros y/u oligomeros, y los monomeros y/u oligomeros reaccionan en la fase llquida continua para dar el pollmero. La invencion se refiere ademas a un reactor para la realizacion del procedimiento y a un uso del procedimiento y reactor.The invention relates to a process for the preparation of polymers from monomers and / or oligomers, in which a liquid containing the monomers and / or oligomers is introduced dropwise into a continuous liquid phase in a reactor, in the that the continuous liquid phase is not miscible with the liquid that contains the monomers and / or oligomers, and the monomers and / or oligomers react in the continuous liquid phase to give the polymer. The invention also relates to a reactor for carrying out the process and a use of the process and reactor.
La preparacion de pollmeros a partir de monomeros y/u oligomeros puede realizarse de manera diversa. As! es posible, por ejemplo, para la preparacion de perlas de pollmero preparar estas mediante una denominada polimerizacion en gotas. En general, para la polimerizacion en gotas se pulveriza el monomero llquido en una fase gaseosa, de manera que se forman gotas individuales. En las gotas reacciona el monomero para dar el pollmero y se forman perlas de pollmero individuales. Sin embargo es un inconveniente de este procedimiento que el tiempo de calda de las gotas en la fase gaseosa permita solo reacciones rapidas. Segun esto se trata, por ejemplo, de la polimerizacion de acido acrllico para dar superabsorbedores.The preparation of polymers from monomers and / or oligomers can be carried out in a different way. Ace! It is possible, for example, for the preparation of polymer beads to prepare these by a so-called drop polymerization. In general, for liquid polymerization, the liquid monomer is sprayed in a gas phase, so that individual drops are formed. In the drops the monomer reacts to give the polymer and individual polymer beads are formed. However, it is a drawback of this procedure that the drop time of the drops in the gas phase allows only rapid reactions. According to this it is, for example, the polymerization of acrylic acid to give superabsorbers.
Ademas de la pulverizacion del monomero llquido es tambien posible anadir gota a gota los monomeros llquidos en un llquido no miscibles con estos. Esto se conoce, por ejemplo, para la preparacion de polimetacrilato por el documento DE-A 30 09 812 o para la preparacion de copollmeros de estireno/divinilbenceno por el documento EP-A 0 173 518. La formacion de gotas del monomero llquido se realiza a este respecto en cada caso directamente en el llquido. Sin embargo, un inconveniente de la generation de gotas en la fase llquida continua es que esta esta limitada a gotas grandes y un control para determinar el tamano de gota es posible solo de manera reducida. Otro inconveniente de la generacion de gotas en la fase continua es que a temperaturas mas altas existe el riesgo de obstruccion de la boquilla.In addition to the spraying of the liquid monomer, it is also possible to add the liquid monomers drop by drop in a liquid not miscible with them. This is known, for example, for the preparation of polymethacrylate by DE-A 30 09 812 or for the preparation of styrene / divinylbenzene copolymers by EP-A 0 173 518. Drop formation of the liquid monomer is carried out. in this respect in each case directly in the liquid. However, a drawback of the drop generation in the continuous liquid phase is that it is limited to large drops and a control to determine the size of the drop is only possible in a reduced manner. Another drawback of the generation of drops in the continuous phase is that at higher temperatures there is a risk of clogging the nozzle.
El objetivo de la presente invencion es facilitar un procedimiento para la preparacion de pollmeros a partir de monomeros y/u oligomeros, que permite la preparacion de partlculas de pollmero en tamano discrecional.The objective of the present invention is to facilitate a process for the preparation of polymers from monomers and / or oligomers, which allows the preparation of polymer particles at discretionary size.
Se soluciona el objetivo mediante un procedimiento para la preparacion de pollmeros a partir de monomeros y/u oligomeros, en el que un llquido que contiene los monomeros y/u oligomeros se introduce gota a gota en una fase llquida continua en un reactor, en el que la fase llquida continua no es miscible con el llquido que contienen los monomeros y/u oligomeros, y los monomeros y/u oligomeros reaccionan en la fase llquida continua para dar el pollmero. El llquido que contiene los monomeros y/u oligomeros se conforma fuera de la fase llquida continua para dar gotas, que se incorporan a continuation en la fase llquida continua.The objective is solved by a process for the preparation of polymers from monomers and / or oligomers, in which a liquid containing the monomers and / or oligomers is introduced dropwise into a continuous liquid phase in a reactor, in the that the continuous liquid phase is not miscible with the liquid contained in the monomers and / or oligomers, and the monomers and / or oligomers react in the continuous liquid phase to give the polymer. The liquid containing the monomers and / or oligomers is formed outside the continuous liquid phase to give drops, which are then incorporated into the continuous liquid phase.
El procedimiento de acuerdo con la invencion permite usar cualquier dispositivo discrecional para la generacion de gotas en la fase gaseosa. Mediante esto es posible ajustar de manera discrecional el tamano de las gotas. Otra ventaja de la generacion de las gotas en la fase gaseosa es que el llquido que va a gotearse en el dispositivo para la generacion de las gotas no tiene ningun contacto con una fase llquida caliente y as! no existe o existe solo un riesgo muy bajo de obstruction de las boquillas. Ademas pueden distribuirse las gotas de manera optima en la fase llquida y puede aprovecharse mejor el volumen de reaction disponible.The method according to the invention allows using any discretionary device for the generation of drops in the gas phase. By this it is possible to adjust the size of the drops discretionally. Another advantage of the generation of the drops in the gas phase is that the liquid to be dripped in the device for the generation of the drops has no contact with a hot liquid phase and so on! There is no or only a very low risk of clogging the nozzles. In addition, the drops can be optimally distributed in the liquid phase and the available reaction volume can be better utilized.
Otra ventaja de la formacion de las gotas fuera de la fase llquida continua es que la formacion de las gotas puede realizarse a una temperatura por debajo de la temperatura de initiation de la reaccion y la reaccion comienza solo en la fase llquida continua. A diferencia de esto, en el caso de una formacion de las gotas en la fase llquida continua, tal como se conoce esta por el estado de la tecnica, puede producirse ya una reaccion en el distribuidor de gotas, de manera que es posible una obstruccion de las boquillas individuales para la generacion de gotas mediante polimerizacion del monomero.Another advantage of the formation of the drops outside the continuous liquid phase is that the formation of the drops can be carried out at a temperature below the temperature of initiation of the reaction and the reaction begins only in the continuous liquid phase. In contrast to this, in the case of a formation of the drops in the continuous liquid phase, as is known by the state of the art, a reaction in the drop dispenser can already occur, so that an obstruction is possible of the individual nozzles for the generation of drops by polymerization of the monomer.
El reactor, en el que se realiza la reaccion, esta configurado como reactor tubular, tal como se define en particular en las reivindicaciones 10 a 13. El tubo del reactor tubular es a este respecto habitualmente un tubo de flujo, por el que fluye la fase llquida continua.The reactor, in which the reaction is carried out, is configured as a tubular reactor, as defined in particular in claims 10 to 13. The tube of the tubular reactor is usually in this respect a flow tube, through which the flow flows. Liquid phase continues.
Mediante la election de un llquido adecuado para la fase llquida continua se evita que las gotas individuales se aglomeren en la superficie de la fase llquida continua. Para ello es ventajoso en particular cuando la fase llquida continua presenta una baja tension superficial, de modo que las gotas que chocan contra la superficie de la fase llquida continua inmediatamente se zambullen en la fase llquida continua.By choosing a suitable liquid for the continuous liquid phase, the individual drops are prevented from agglomerating on the surface of the continuous liquid phase. This is particularly advantageous when the continuous liquid phase has a low surface tension, so that the drops that collide with the surface of the continuous liquid phase immediately dive into the continuous liquid phase.
En una primera forma de realizacion fluyen las gotas del llquido que contiene los monomeros y/u oligomeros y la fase llquida continua en contracorriente. Para que las gotas del llquido que contiene los monomeros y/u oligomeros y la fase llquida continua fluyan en contracorriente, es necesario que sobre las gotas se aplique una fuerza motriz paraIn a first embodiment, the drops of the liquid containing the monomers and / or oligomers flow and the liquid phase continues in countercurrent. In order for the drops of the liquid containing the monomers and / or oligomers and the continuous liquid phase to flow in countercurrent, it is necessary that a driving force be applied on the drops
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el flujo. Esta puede ser por ejemplo la fuerza de gravedad y el movimiento de las gotas puede realizarse mediante hundimiento en la fase llquida continua. En este caso debe seleccionarse la velocidad de la fase llquida continua de modo que las gotas que se hunden en la fase llquida continua no se arrastran con la fase llquida continua. Mediante una contracorriente de las gotas a partir del llquido que contiene los monomeros y/u oligomeros y la fase llquida continua puede conseguirse en espacio constructivo relativamente corto un tiempo de permanencia comparativamente alto.the flow. This can be, for example, the force of gravity and the movement of the drops can be carried out by sinking in the continuous liquid phase. In this case, the speed of the continuous liquid phase must be selected so that the drops that sink into the continuous liquid phase do not creep with the continuous liquid phase. By means of a countercurrent of the drops from the liquid containing the monomers and / or oligomers and the continuous liquid phase, a comparatively high residence time can be achieved in a relatively short construction space.
Sin embargo se prefiere que las gotas del llquido que contiene los monomeros y/u oligomeros y la fase llquida continua fluyan en corriente directa. En este caso, las gotas del llquido que contiene los monomeros y/u oligomeros se arrastran por la fase llquida continua. Esto tiene ademas la ventaja de que la forma del tubo de flujo en el que se realiza la reaccion puede configurarse de manera variable. As! es posible, por ejemplo, configurar el tubo por el que fluye el llquido continuo en forma de meandro para reducir la altura de construccion. Tambien es posible configurar el tubo, por ejemplo, en forma de espiral. Tambien es concebible cualquier otra geometrla discrecional del tubo de flujo, en el que fluye la fase llquida continua con las gotas del llquido que contiene los monomeros y/u oligomeros. Debido a las geometrlas variables del tubo de flujo pueden realizarse tiempos de permanencia discrecionales mediante distintas longitudes del tubo. Ademas pueden realizarse distintos tiempos de permanencia tambien debido a que se adapta la velocidad de flujo de la fase llquida continua.However, it is preferred that the drops of the liquid containing the monomers and / or oligomers and the continuous liquid phase flow in direct current. In this case, the drops of the liquid containing the monomers and / or oligomers are carried along the continuous liquid phase. This also has the advantage that the shape of the flow tube in which the reaction is carried out can be configured in a variable manner. Ace! it is possible, for example, to configure the tube through which the continuous liquid flows in the form of a meander to reduce the height of construction. It is also possible to configure the tube, for example, in the form of a spiral. Any other discretionary geometry of the flow tube is also conceivable, in which the liquid phase flows continuously with the drops of the liquid containing the monomers and / or oligomers. Due to the variable geometries of the flow tube discretionary residence times can be made by different lengths of the tube. In addition, different residence times can be carried out also because the flow rate of the continuous liquid phase is adapted.
La alimentacion de la fase llquida continua en el reactor configurado como tubo de flujo se realiza preferentemente por debajo de los medios, con los que el llquido que contiene los monomeros y/u oligomeros se introduce gota a gota. La alimentacion puede encontrarse a este respecto por encima del nivel del llquido de la fase llquida continua o a la altura del nivel del llquido de la fase llquida continua. Tambien es concebible una posicion por debajo de la superficie de la fase llquida continua. Se prefiere, sin embargo, una disposition por encima de la superficie de la fase llquida continua o a la altura de la superficie de la fase llquida continua.The continuous liquid phase feeding into the reactor configured as a flow tube is preferably carried out below the means, with which the liquid containing the monomers and / or oligomers is introduced dropwise. The feed may be in this respect above the level of the liquid of the continuous liquid phase or at the level of the liquid level of the continuous liquid phase. A position below the surface of the continuous liquid phase is also conceivable. However, an arrangement above the surface of the continuous liquid phase or at the height of the surface of the continuous liquid phase is preferred.
Antes de que el llquido se separe de nuevo del tubo de flujo que sirve como reactor, se extraen las partlculas de pollmero que se han formado mediante reaccion de los monomeros y/u oligomeros contenidos en las gotas. La separation se realiza a este respecto por ejemplo mediante una separation de solido/llquido discrecional conocida por el experto. La separacion de solido/llquido puede realizarse, por ejemplo, mediante filtros, tamices, centrlfugas adecuados o tambien por ejemplo mediante un hidrociclon. Cuando se usan filtros para la separacion, son adecuados por ejemplo filtros de banda o filtro rotativo a presion. Ademas es adecuada por ejemplo tambien una centrlfuga de empuje.Before the liquid separates again from the flow tube that serves as the reactor, the polymer particles that have been formed are removed by reacting the monomers and / or oligomers contained in the drops. The separation is carried out in this respect for example by means of a discretionary solid / liquid separation known to the expert. The solid / liquid separation can be carried out, for example, by suitable filters, sieves, centrifuges or also for example by a hydrocyclone. When filters are used for separation, for example band filters or rotary pressure filter are suitable. In addition, a thrust centrifuge is also suitable.
Cuando se usa un filtro para la separacion de las partlculas de pollmero, se realiza la filtration en particular en la preparation de poliamidas a una temperatura de mas de 80 °C, dado que en caso contrario precipita caprolactama y puede obstruirse el filtro.When a filter is used for the separation of the polymer particles, filtration is carried out in particular in the preparation of polyamides at a temperature of more than 80 ° C, since otherwise caprolactam precipitates and the filter can become clogged.
Para separar la fase llquida continua, por ejemplo el aceite blanco de las partlculas de pollmero tras la filtracion, se lavan preferentemente las partlculas de pollmero. Como llquido de lavado es adecuado por ejemplo acetato de butilo.To separate the continuous liquid phase, for example the white oil from the polymer particles after filtration, the polymer particles are preferably washed. As a washing liquid, for example, butyl acetate is suitable.
Tras la separacion de las partlculas de solido se conduce la fase llquida de nuevo a traves de la alimentacion al reactor. Para evitar que actuen fuerzas de cizallamiento sobre las gotas o las partlculas de pollmero preparadas a partir de las gotas, estan colocados medios, con los que se mueve la fase llquida continua, por ejemplo bombas, fuera del reactor que sirve como tubo de flujo. Las bombas pueden estar dispuestas, por ejemplo, directamente delante de la alimentacion o directamente tras la separacion de solido/llquido. Sin embargo es tambien posible colocar la bomba en cualquier otra posicion discrecional en la conduction de conexion entre el sitio de extraction de la fase llquida continua y la alimentacion de la fase llquida continua en el reactor.After separation of the solid particles, the liquid phase is conducted again through the feed to the reactor. To prevent shear forces from acting on the drops or polymer particles prepared from the drops, means are placed, with which the continuous liquid phase, for example pumps, moves out of the reactor that serves as a flow tube. The pumps may be arranged, for example, directly in front of the feed or directly after solid / liquid separation. However, it is also possible to place the pump in any other discretionary position in the connection line between the extraction site of the continuous liquid phase and the supply of the continuous liquid phase in the reactor.
Como alternativa a una fase llquida continua que fluye, ya sea en corriente directa o en contracorriente con respecto a las gotas a partir del llquido que contiene los monomeros y/u oligomeros, es posible tambien que la fase llquida continua no fluya. En este caso es necesario sin embargo que el reactor este configurado como tubo vertical o como columna, para que las gotas no puedan hundirse hacia abajo en el llquido que no fluye debido a la fuerza de la gravedad. En este caso, el reactor presenta una alimentacion, mediante la que puede complementarse llquido, que se descarga por ejemplo mediante evaporation o mediante la extraccion de las partlculas de pollmero preparadas.As an alternative to a continuous liquid phase that flows, either in direct current or in countercurrent with respect to the drops from the liquid containing the monomers and / or oligomers, it is also possible that the continuous liquid phase does not flow. In this case, however, it is necessary that the reactor be configured as a vertical tube or as a column, so that the drops cannot sink down into the liquid that does not flow due to the force of gravity. In this case, the reactor has a feed, by which liquid can be supplemented, which is discharged for example by evaporation or by extracting the prepared polymer particles.
Dado que la reaccion de los monomeros y/u oligomeros para dar los pollmeros se realiza generalmente a temperatura elevada, se prefiere calentar la fase llquida continua. Para ello es posible, por ejemplo, configurar el reactor con un revestimiento doble como pared y calentarlo a traves del revestimiento doble. Para ello se hace fluir por el revestimiento doble un medio de calentamiento. Como alternativa es concebible tambien cualquier otro tipo discrecional de calentamiento. As! es posible, por ejemplo, tambien calentar electricamente el revestimiento doble usando elementos de calefaccion adecuados. Tambien es concebible que en el tubo esten alojados elementos de calefaccion que calientan la fase llquida continua. La temperatura, hasta la que se calienta la fase llquida continua depende, a este respecto, de la reaccion realizada en el reactor.Since the reaction of the monomers and / or oligomers to give the polymers is generally carried out at elevated temperature, it is preferred to heat the continuous liquid phase. For this, it is possible, for example, to configure the reactor with a double lining as a wall and heat it through the double liner. For this, a heating medium is flowed through the double coating. Alternatively, any other discretionary type of heating is conceivable. Ace! It is also possible, for example, to electrically heat the double lining using suitable heating elements. It is also conceivable that heating elements that heat the continuous liquid phase are housed in the tube. The temperature to which the continuous liquid phase is heated depends, in this respect, on the reaction carried out in the reactor.
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En comparacion con una polimerizacion en gotas en la fase gaseosa es mas grande el tiempo de permanencia en el llquido. Por consiguiente pueden realizarse tambien reacciones que discurran menos rapidamente. En comparacion con los procedimientos de polimerizacion clasicos, por ejemplo polimerizacion en solucion, polimerizacion con precipitacion, polimerizacion en masa, polimerizacion en suspension, polimerizacion en emulsion, que se realizan por ejemplo en un recipiente agitador o un reactor tubular, son estas reacciones sin embargo todavla muy rapidas. Mediante la gran superficie especlfica de las gotas pueden controlarse altas entalpias, de manera que son posibles una alta cinetica de reaccion, un gran tono termico y un alto contenido en solidos. Debido a la gran superficie especlfica de las gotas se impide un sobrecalentamiento o fuga de la reaccion.Compared with a drop polymerization in the gas phase, the residence time in the liquid is longer. Consequently, reactions that run less rapidly can also be performed. In comparison with the classical polymerization processes, for example solution polymerization, precipitation polymerization, mass polymerization, suspension polymerization, emulsion polymerization, which are carried out for example in an agitator vessel or a tubular reactor, these reactions are however still very fast. High enthalpies can be controlled by the large specific surface of the drops, so that a high reaction kinetics, a great thermal tone and a high solids content are possible. Due to the large specific surface of the drops, overheating or reaction leakage is prevented.
Otra ventaja del procedimiento de acuerdo con la invencion es que no es necesario usar agentes adicionales, mediante los cuales se evite una coalescencia de gotas. Tales agentes son por ejemplo tensioactivos, con los que se reduce la tension superficial.Another advantage of the process according to the invention is that it is not necessary to use additional agents, by which a coalescence of drops is avoided. Such agents are for example surfactants, with which the surface tension is reduced.
La generation de las gotas a partir del llquido que contiene los monomeros y/u oligomeros puede realizarse de cualquier modo discrecional, conocido por el experto. Habitualmente se usan procedimientos para la generacion de gotas, mediante los cuales se generan gotas en la fase gaseosa. Los procedimientos adecuados son por ejemplo boquillas o tambien perforaciones en una placa de formation de gotas, tal como se reivindican en la revindication 4. Cuando se usan boquillas, es adecuada cualquier forma de boquilla discrecional, mediante la cual se generan gotas.The generation of the drops from the liquid containing the monomers and / or oligomers can be carried out in any discretionary manner, known to the expert. Usually procedures are used for the generation of drops, by which drops are generated in the gas phase. Suitable procedures are for example nozzles or also perforations in a drop formation plate, as claimed in revindication 4. When nozzles are used, any form of discretionary nozzle, by which drops are generated, is suitable.
Para la generacion de las gotas pueden usarse por ejemplo una o varias boquillas pulverizadoras. A este respecto es posible usar cualquier boquilla pulverizadora discrecional, conocida por el experto. A las boquillas pulverizadoras de este tipo puede alimentarse el llquido que va a pulverizarse con presion. La division del llquido que va a pulverizarse en gotas individuales se realiza a este respecto, por ejemplo, debido a que tras alcanzar una velocidad minima predeterminada se distiende el llquido en el orificio de la boquilla. Tambien es posible usar boquillas de una sola sustancia, por ejemplo boquillas ranuradas o boquillas de cono lleno.For example, one or more spray nozzles can be used for the generation of the drops. In this regard it is possible to use any discretionary spray nozzle, known to the expert. The liquid to be sprayed with pressure can be fed to the spray nozzles of this type. The division of the liquid to be sprayed into individual drops is done in this respect, for example, because after reaching a predetermined minimum speed the liquid in the nozzle orifice is distended. It is also possible to use single substance nozzles, for example slotted nozzles or full cone nozzles.
Se prefiere especialmente el uso de boquillas de cono lleno. Entre estas se prefieren especialmente aquellas con un angulo de abertura del cono pulverizador de 60 ° a 180 °. En particular se prefieren boquillas de cono lleno con un angulo de abertura en el intervalo de 90 ° a 120 °. El diametro de gota que se ajusta en la pulverization se encuentra preferentemente en el intervalo de 10 a 1000 pm, preferentemente en el intervalo de 50 a 500 pm, en particular en el intervalo de 100 a 200 pm. El diametro de gota puede determinarse segun procedimientos conocidos por el experto, por ejemplo dispersion de luz, o por medio de lineas caracteristicas que pueden obtenerse por parte del fabricante de boquillas. El caudal de cada boquilla pulverizadora usada individual se encuentra preferentemente en el intervalo de 0,1 a 10 m3/h, en particular en el intervalo de 0,5 a 5 m3/h.The use of full cone nozzles is especially preferred. Among these, those with an opening angle of the spray cone of 60 ° to 180 ° are especially preferred. In particular, full cone nozzles with an opening angle in the range of 90 ° to 120 ° are preferred. The drop diameter that is adjusted in the pulverization is preferably in the range of 10 to 1000 pm, preferably in the range of 50 to 500 pm, in particular in the range of 100 to 200 pm. The drop diameter can be determined according to procedures known to the expert, for example light scattering, or by means of characteristic lines that can be obtained by the nozzle manufacturer. The flow rate of each individual spray nozzle used is preferably in the range of 0.1 to 10 m3 / h, in particular in the range of 0.5 to 5 m3 / h.
Como alternativa al uso de boquillas pulverizadoras es tambien posible usar dispositivos en los que pueda caer libremente el llquido que contiene los monomeros y/u oligomeros en forma de gotas monodispersas. Un dispositivo de este tipo se ha descrito por ejemplo en el documento US 5.269.980. Ademas es posible tambien una generacion de gotas mediante desintegracion por chorro laminar, por ejemplo tal como se describe en Rev. Sci. Instr. 38(1966) 502.As an alternative to the use of spray nozzles it is also possible to use devices in which the liquid containing the monomers and / or oligomers in the form of monodisperse drops can freely fall. Such a device has been described for example in US 5,269,980. In addition, it is also possible to generate drops by means of disintegration by laminar jet, for example as described in Rev. Sci. Instr. 38 (1966) 502.
El uso de una placa de formacion de gotas con perforaciones es adecuada en particular para llquidos viscosos. El tamano de las perforaciones se selecciona entonces de modo que no salga un chorro de llquido por las perforaciones, sino gotas individuales. Para ello se encuentra por encima de la placa de formacion de gotas una reserva de llquido, que contiene el llquido que contiene los monomeros y/u oligomeros. Desde la reserva de llquido se escurre llquido a traves de las perforaciones en la placa de formacion de gotas y gotea desde esta en la fase llquida continua.The use of a drop forming plate with perforations is particularly suitable for viscous liquids. The size of the perforations is then selected so that a liquid jet does not flow out of the perforations, but rather individual drops. For this purpose, a liquid reservoir, containing the liquid containing the monomers and / or oligomers, is located above the drop-forming plate. Liquid is drained from the liquid reservoir through the perforations in the drop-forming plate and drips from it in the continuous liquid phase.
Igualmente es adecuado la generacion de las gotas mediante boquillas de estiraje neumaticas, rotation, corte de un chorro o boquillas con microvalvulas que pueden accionarse rapidamente.Equally suitable is the generation of the drops by pneumatic stretching nozzles, rotation, cutting of a jet or nozzles with microvalves that can be operated quickly.
En la generacion de gotas en una boquilla de estiraje neumatica se acelera un chorro de llquido junto con un flujo de gas mediante un diafragma. A traves de la cantidad de gas usada puede verse influido el diametro del chorro de liquido y con ello tambien el diametro de gota.In the generation of drops in a pneumatic stretching nozzle, a liquid jet is accelerated together with a gas flow through a diaphragm. Through the amount of gas used, the diameter of the liquid jet can be influenced and thus also the drop diameter.
En la generacion de gotas mediante rotacion sale el liquido por las aberturas de un disco giratorio. Mediante la fuerza centrifuga que actua sobre el liquido se arrancan gotas de tamano definido. Cuando las gotas se generan mediante corte de un chorro, entonces puede cortarse por ejemplo un liquido que sale de una abertura o boquilla con una cuchilla giratoria en segmentos definidos. A este respecto forma cada segmento a continuation una gota.In the generation of drops by rotation, the liquid flows through the openings of a rotating disk. By means of the centrifugal force that acts on the liquid drops of defined size are started. When the drops are generated by cutting a jet, then, for example, a liquid leaving an opening or nozzle can be cut with a rotating blade in defined segments. In this respect, each segment then forms a drop.
Con el uso de boquillas con microvalvulas se generan directamente gotas con volumen de liquido definido.With the use of nozzles with microvalves, drops with a defined liquid volume are generated directly.
Cuando el llquido que contiene los monomeros y/u oligomeros se dosifica por al menos una perforation en una placa de formacion de gotas con formacion de gotas, es ventajoso desplazar la placa de formacion de gotas o elWhen the liquid containing the monomers and / or oligomers is dosed by at least one perforation in a drop-forming plate with drop formation, it is advantageous to move the drop-forming plate or the
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llquido en oscilaciones, de manera que en el lado inferior de la placa de formacion de gotas se genera por perforacion una cadena de gotas monodispersa de manera ideal. Sin embargo se prefiere no excitar la placa de formacion de gotas.liquid in oscillations, so that a monodisperse drop chain is ideally drilled on the lower side of the drop-forming plate. However, it is preferred not to excite the drop-forming plate.
El numero y el tamano de las perforaciones en la placa de formacion de gotas se seleccionan de acuerdo con la capacidad y el tamano de gota deseados. El diametro de gota asciende a este respecto habitualmente a 1,9 veces el diametro de la perforacion. Segun esto ha de tenerse en cuenta que el llquido que va a gotearse no salga demasiado rapido por la perforacion o que la perdida de presion a traves de la perforacion no sea demasiado grande. En caso contrario el llquido no gotea, sino que el chorro de llquido se divide como consecuencia de la alta energla cinetica, es decir se pulveriza. El Indice de Reynold con respecto al caudal por perforacion y el diametro de perforacion es preferentemente <2000, mas preferentemente <1600, de manera especialmente preferente <1400 y de manera muy especialmente preferente <1200.The number and size of the perforations in the drop forming plate are selected according to the desired capacity and drop size. The drop diameter usually amounts to 1.9 times the diameter of the perforation. According to this, it should be taken into account that the liquid to be dripped does not come out too quickly due to the perforation or that the loss of pressure through the perforation is not too large. Otherwise the liquid does not drip, but the liquid jet is divided as a result of high kinetic energy, that is, it is sprayed. The Reynold Index with respect to the flow rate by drilling and the drilling diameter is preferably <2000, more preferably <1600, especially preferably <1400 and very especially preferably <1200.
Las placas de formacion de gotas usadas para el procedimiento de acuerdo con la invencion presentan al menos una, preferentemente al menos 10 y en particular al menos 50 hasta 10.000, preferentemente hasta 5000 y en particular hasta 1000 perforaciones, estando distribuidas las perforaciones ventajosamente de manera uniforme por la placa de formacion de gotas. La distribution se realiza a este respecto preferentemente en la denominada division triangular, en la que en cada caso tres perforaciones forman las esquinas de un triangulo equilatero.The drop-forming plates used for the process according to the invention have at least one, preferably at least 10 and in particular at least 50 to 10,000, preferably up to 5000 and in particular up to 1000 perforations, the perforations being advantageously distributed so uniform by the drop formation plate. The distribution is carried out in this respect preferably in the so-called triangular division, in which in each case three perforations form the corners of an equilateral triangle.
La distancia de las perforaciones se encuentra preferentemente en el intervalo de 1 a 50 mm, de manera especialmente preferente en el intervalo de 2,5 a 20 mm y en particular en el intervalo de 5 a 10 mm.The distance of the perforations is preferably in the range of 1 to 50 mm, especially preferably in the range of 2.5 to 20 mm and in particular in the range of 5 to 10 mm.
Independientemente del tipo de medios usados para la generation de gotas, la distancia entre los medios para la generation de gotas y la fase llquida continua se encuentra preferentemente en el intervalo de 20 a 500 mm, mas preferentemente en el intervalo de 30 a 200 mm y en particular en el intervalo de 50 a 150 mm.Regardless of the type of means used for the generation of drops, the distance between the means for the generation of drops and the continuous liquid phase is preferably in the range of 20 to 500 mm, more preferably in the range of 30 to 200 mm and in particular in the range of 50 to 150 mm.
Dependiendo del medio usado para la generacion de gotas as! como de la viscosidad del llquido que contiene los monomeros y/u oligomeros puede verse influido el tamano de la gota. La viscosidad del llquido que contiene los monomeros y/u oligomeros puede ajustarse a este respecto, por ejemplo, usando disolventes, en los que se dispersan los monomeros y/u oligomeros. Sin embargo se prefiere usar un llquido que contenga solo monomeros y/u oligomeros y ningun disolvente. Esto tiene la ventaja de que tras finalizar la reaction no debe separarse ningun disolvente adicional de la fase llquida continua o del pollmero generado. Cuando los monomeros y/u oligomeros se usan sin disolvente adicional, esto tiene la ventaja de que tras finalizar la reaccion de polimerizacion unicamente deben separarse la fase llquida continua y las partlculas de pollmero uno de otro mediante una separation de solido/llquido discrecional y deben secarse las partlculas a continuation. El secado puede realizarse por ejemplo mediante gasificado con nitrogeno. Sin embargo es tambien posible cualquier otro tipo de secado discrecional que el experto conozca. Segun esto ha de prestarse atencion unicamente a que la atmosfera en la que se secan las partlculas de pollmero sea inerte.Depending on the medium used for the generation of drops ace! As the viscosity of the liquid containing the monomers and / or oligomers, the size of the drop can be influenced. The viscosity of the liquid containing the monomers and / or oligomers can be adjusted in this respect, for example, using solvents, in which the monomers and / or oligomers are dispersed. However, it is preferred to use a liquid containing only monomers and / or oligomers and no solvent. This has the advantage that after completion of the reaction, no additional solvent must be separated from the continuous liquid phase or from the polymer generated. When the monomers and / or oligomers are used without additional solvent, this has the advantage that after completion of the polymerization reaction only the continuous liquid phase and the polymer particles must be separated from each other by a discretionary solid / liquid separation and must Dry the particles next. Drying can be carried out, for example, by gasification with nitrogen. However, any other type of discretionary drying that the expert knows is also possible. According to this, attention should be paid only to the atmosphere in which the polymer particles are dried is inert.
Las reacciones que se realizan para la preparation de pollmeros con el procedimiento de acuerdo con la invencion pueden ser todas las reacciones mediante las cuales pueden prepararse pollmeros. As! puede aplicarse el procedimiento, por ejemplo, para polimerizaciones ionicas o por radicales, poliadiciones o policondensaciones. En particular con el uso del procedimiento para policondensaciones es especialmente ventajoso cuando la fase llquida continua contiene el mismo llquido que se separa tambien en la policondensacion.The reactions that are carried out for the preparation of polymers with the process according to the invention can be all the reactions by which polymers can be prepared. Ace! the procedure can be applied, for example, for ionic or radical polymerizations, polyamines or polycondensations. Particularly with the use of the polycondensation procedure is especially advantageous when the continuous liquid phase contains the same liquid that also separates in the polycondensation.
Dependiendo del pollmero que va a prepararse, el llquido que contiene monomeros y/u oligomeros puede contener solo un tipo de monomeros y/u oligomeros o distintos monomeros y/u oligomeros. Cuando estan contenidos distintos monomeros y/u oligomeros, entonces pueden presentar estos o bien distintos grupos funcionales, que reaccionan entre si y as! forman una cadena o se usan monomeros y comonomeros para la preparacion de copollmeros. De manera especialmente preferente se usa el procedimiento para la preparacion de poliamidas. En la preparacion de poliamidas reaccionan habitualmente dos unidades monomericas distintas para dar el pollmero. A continuacion se designan las distintas unidades monomericas como monomero y comonomero. El llquido que contiene monomeros contiene en particular monomeros y comonomeros, que reaccionan entre si para dar el pollmero.Depending on the polymer to be prepared, the liquid containing monomers and / or oligomers may contain only one type of monomers and / or oligomers or different monomers and / or oligomers. When different monomers and / or oligomers are contained, then they can present these or different functional groups, which react with each other and so! they form a chain or monomers and comonomers are used for the preparation of copolymers. Especially preferably, the process for the preparation of polyamides is used. In the preparation of polyamides, two different monomer units react to give the polymer. The different monomer units are then designated as monomer and comonomer. The liquid containing monomers contains in particular monomers and comonomers, which react with each other to give the polymer.
El procedimiento se define ademas en las reivindicaciones 7 a 9.The procedure is further defined in claims 7 to 9.
En la preparacion de poliamidas se seleccionan los monomeros por ejemplo del grupo que esta constituido por caprolactama, caprolactona y laurinlactama y los comonomeros se seleccionan del grupo que esta constituido por caprolactama, caprolactona, laurinlactama, politetrahidrofurano y aminocaprolactama.In the preparation of polyamides, the monomers are selected, for example, from the group consisting of caprolactam, caprolactone and laurinlactam and the comonomers are selected from the group consisting of caprolactam, caprolactone, laurinlactam, polytetrahydrofuran and aminocaprolactam.
Ademas de la preparacion de poliamidas es posible sin embargo tambien la preparacion de cualquier otro pollmero. As! puede usarse el procedimiento de acuerdo con la invencion o un reactor tubular en particular tambien para la preparacion de poli(met)acrilatos, tal como se usan estos por ejemplo como superabsorbedores.In addition to the preparation of polyamides, however, it is also possible to prepare any other polymer. Ace! The process according to the invention or a tubular reactor in particular can also be used for the preparation of poly (meth) acrylates, as these are used for example as superabsorbers.
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Ademas puede usarse el procedimiento de acuerdo con la invencion o un reactor tubular tambien para la preparacion de poliestireno, polivinilpirrolidona, poliacrilamida, poli(alcohol vinllico), poli(acido acrllico), polivinilaminas, poli(acido maleico), poli(acrilato de butilo), policaprolactonas y poliuretanos termoplasticos.In addition, the process according to the invention or a tubular reactor can also be used for the preparation of polystyrene, polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol, poly (acrylic acid), polyvinylamines, poly (maleic acid), poly (butyl acrylate) ), thermoplastic polycaprolactones and polyurethanes.
En una forma de realizacion de la invencion es tambien posible preparar partlculas encapsuladas. Como materiales de encapsulacion para la envoltura de las partlculas de pollmero encapsuladas son adecuados basicamente todos los materiales que no se disuelven o no se disuelven parcialmente por la fase llquida interna. Como materiales para la envoltura pueden usarse por ejemplo tambien homo- o copollmeros de los monomeros que van a polimerizarse, siempre que estos se comporten como no solubles frente a la fase llquida interna. La fase llquida interna es a este respecto el llquido que contiene monomeros y/u oligomeros. As! es posible, por ejemplo, usar en la preparacion de poliestireno un poliestireno ya polimerizado como material de envoltura. A este respecto puede usarse el poliestireno en forma de una masa fundida.In an embodiment of the invention it is also possible to prepare encapsulated particles. As encapsulation materials for wrapping the encapsulated polymer particles, all materials that do not dissolve or partially dissolve through the internal liquid phase are suitable. As wrapping materials, for example, homo- or copolymers of the monomers to be polymerized can also be used, provided that they behave as not soluble against the internal liquid phase. The internal liquid phase is in this respect the liquid that contains monomers and / or oligomers. Ace! It is possible, for example, to use an already polymerized polystyrene in the preparation of polystyrene as the wrapping material. In this respect, polystyrene can be used in the form of a melt.
Ademas, en la preparacion de pollmeros a base de N-vinilpirrolidona puede usarse una polivinilpirrolidona como material de envoltura, pudiendose usar la polivinilpirrolidona en forma de una solucion. Tambien son adecuados pollmeros termoplasticos como polietersulfonas, polisulfonas o policaprolactonas.In addition, in the preparation of polymers based on N-vinyl pyrrolidone a polyvinyl pyrrolidone can be used as the wrapping material, the polyvinyl pyrrolidone being used as a solution. Thermoplastic polymers such as polyethersulfones, polysulfones or polycaprolactones are also suitable.
Ademas son adecuados como materiales de envoltura ceras como cera de parafina, que pueden gotearse en forma de una masa fundida.Also suitable as wrapping materials are waxes such as paraffin wax, which can drip in the form of a melt.
Los pollmeros pueden usarse como solucion acuosa o en forma de una masa fundida. A este respecto pueden presentar los materiales de envoltura puntos de fusion en el intervalo de 20 a 220 °C, preferentemente en el intervalo de 60 a 200 °C.The polymers can be used as an aqueous solution or in the form of a melt. In this regard, the wrapping materials may have melting points in the range of 20 to 220 ° C, preferably in the range of 60 to 200 ° C.
Para obtener partlculas de pollmero encapsuladas, se introducen gota a gota preferentemente gotas dobles en la fase llquida continua, presentando las gotas dobles un nucleo constituido por el llquido que contiene los monomeros y/u oligomeros y una envoltura externa de un material de encapsulacion o un precursor del material de encapsulacion. Las gotas dobles deben generarse a este respecto preferentemente como gotas mononucleares. En una gota doble de este tipo se encuentra el nucleo centrado en el interior de la microcapsula y se envuelve por el revestimiento. Los dispositivos adecuados, con los que pueden generarse tales gotas dobles, son por ejemplo boquillas de varias sustancias, preferentemente aquellas con desintegracion del chorro laminar. En particular son adecuadas las boquillas de rendija anular. Las boquillas de rendija anular de este tipo comprenden en general una boquilla interna que se encuentra centrada, por la que se conduce el llquido que contiene monomeros y/u oligomeros como material de nucleo y una rendija de boquilla anular dispuesta de manera concentrica con respecto a esto para el material de encapsulacion o el precursor del material de encapsulacion. Las boquillas de varias sustancias pueden accionarse tambien de modo que la formacion de gotas se realiza mediante desintegracion de chorro laminar.To obtain encapsulated polymer particles, double drops are preferably introduced dropwise into the continuous liquid phase, the double drops having a core consisting of the liquid containing the monomers and / or oligomers and an outer shell of an encapsulation material or a precursor of the encapsulation material. Double drops should be generated in this respect preferably as mononuclear drops. In a double drop of this type is the nucleus centered inside the microcapsule and is wrapped by the coating. Suitable devices, with which such double droplets can be generated, are for example nozzles of various substances, preferably those with disintegration of the laminar jet. In particular, the annular slit nozzles are suitable. The annular slit nozzles of this type generally comprise an internal nozzle that is centered, through which the liquid containing monomers and / or oligomers is conducted as the core material and an annular nozzle slit arranged concentrically with respect to this for the encapsulation material or the precursor of the encapsulation material. The nozzles of various substances can also be operated so that the formation of drops is carried out by means of disintegration of the laminar jet.
La formacion de gotas puede estar asistida, por ejemplo, mediante la aplicacion de una oscilacion, por ejemplo de una oscilacion sinusoidal. En este denominado procedimiento de vibracion se excita toda la boquilla de varias sustancias mediante un excitador oscilante. Las frecuencias pueden encontrarse a este respecto en el intervalo de 50 a 20.000 Hz. Las gotas dobles formadas de esta manera pueden solidificarse tras abandonar el reactor o bien en una pila de curado o pueden atravesar un segmento de refrigeracion para solidificar el material de revestimiento.The formation of drops may be assisted, for example, by the application of an oscillation, for example of a sinusoidal oscillation. In this so-called vibration procedure, the entire nozzle of several substances is excited by means of an oscillating exciter. Frequencies in this regard can be found in the range of 50 to 20,000 Hz. The double drops formed in this way can solidify after leaving the reactor either in a curing cell or they can pass through a cooling segment to solidify the coating material.
Debido a la envoltura no es necesario que los monomeros y/u oligomeros, que estan contenidos en el interior de la envoltura, se hagan reaccionar ya completamente en el reactor para dar pollmeros. La polimerizacion posterior puede realizarse tambien a continuacion de la solidificacion de la envoltura o en cualquier otro momento posterior.Due to the envelope it is not necessary that the monomers and / or oligomers, which are contained inside the envelope, are already fully reacted in the reactor to give polymers. Subsequent polymerization can also be carried out following solidification of the envelope or at any other later time.
EjemplosExamples
Ejemplo 1Example 1
Una solucion al 17-19 % que contiene caprolactamato de Na en caprolactama (Bruggolen C20 de la empresa Bruggemann) se mezcla con una solucion que contiene diisocianato bloqueado en caprolactama. La solucion que contiene el diisocianato bloqueado contiene aproximadamente un 17 % de grupos NCO (Bruggolen C10 de la empresa Bruggemann). Las dos soluciones se mezclan entre si en una proporcion de 7 con respecto a 1.A 17-19% solution containing Caprolactam Na caprolactamate (Bruggolen C20 from Bruggemann) is mixed with a solution containing caprolactam blocked diisocyanate. The solution containing the blocked diisocyanate contains approximately 17% of NCO groups (Bruggolen C10 from Bruggemann). The two solutions are mixed together in a proportion of 7 with respect to 1.
Mediante un capilar se anade gota a gota la mezcla en aceite blanco caliente a 130 °C. La distancia entre el capilar y el aceite blanco asciende a 50 mm.Using a capillary, the mixture is added dropwise in warm white oil at 130 ° C. The distance between the capillary and the white oil amounts to 50 mm.
El aceite blanco esta contenido en una columna de vidrio de 1500 mm de altura, en la que se bombea el aceite blanco en clrculo de arriba abajo y se conduce a traves de un filtro para la deposicion de solidos.The white oil is contained in a 1500 mm high glass column, in which the white oil is pumped up and down and conducted through a filter for the deposition of solids.
El tiempo de permanencia de las gotas individuales en la columna de vidrio asciende a 20 segundos. Un analisis de las partlculas de pollmero extraldas da como resultado un contenido en caprolactama residual del 2 %, un Indice de viscosidad (VZ), medido segun la norma DIN 1628-1 con un viscoslmetro Ubbelohde tipo DIN-II con una constanteThe residence time of the individual drops in the glass column is 20 seconds. An analysis of the extracted polymer particles results in a residual caprolactam content of 2%, a Viscosity Index (VZ), measured according to DIN 1628-1 with a Ubbelohde viscometer type DIN-II with a constant
capilar de 0,0996, a una temperatura de 25 °C y acido sulfurico al 96 % como disolvente, de 120 ml/g y un tamano de partlcula promedio de 750 pm.0.0996 capillary, at a temperature of 25 ° C and 96% sulfuric acid as solvent, of 120 ml / g and an average particle size of 750 pm.
Ejemplo 2Example 2
Se realiza una reaccion tal como se describe en el ejemplo 1, sin embargo asciende el tiempo de permanencia de 5 las gotas en la columna de vidrio a 50 segundos. En este caso asciende el contenido residual de caprolactama al 1 %, el Indice de viscosidad se encuentra en 170 ml/g y el diametro de partlcula promedio asciende igualmente a 750 pm.A reaction is carried out as described in example 1, however the residence time of 5 drops in the glass column increases to 50 seconds. In this case the residual content of caprolactam rises to 1%, the viscosity index is 170 ml / g and the average particle diameter also amounts to 750 pm.
Ejemplo 3Example 3
A diferencia del ejemplo 2 se realiza un tiempo de permanencia mas largo en el filtro. En este caso resulta un 10 contenido en caprolactama residual del 0,4 %, el Indice de viscosidad se encuentra en 170 ml/g y el diametro de partlcula promedio en 750 pm.Unlike example 2, a longer residence time is carried out in the filter. In this case, a residual caprolactam content of 0.4% results, the viscosity index is 170 ml / g and the average particle diameter is 750 pm.
Claims (14)
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| EP09151847 | 2009-02-02 | ||
| PCT/EP2010/051146 WO2010086433A1 (en) | 2009-02-02 | 2010-02-01 | Method for producing polymers and reactor for carrying out said method |
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| ES2637548T3 true ES2637548T3 (en) | 2017-10-13 |
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| EP (1) | EP2391668B1 (en) |
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|---|---|---|---|---|
| ES2639062T3 (en) | 2009-12-08 | 2017-10-25 | Basf Se | Process for the preparation of polyamides |
| US9181136B2 (en) | 2010-01-19 | 2015-11-10 | Basf Se | Method for producing hollow bodies having enclosed freely displaceable particles |
| CN105601911B (en) * | 2010-10-07 | 2018-07-10 | 巴斯夫欧洲公司 | Prepare the method for monomer composition and its purposes in polyamide molded parts are prepared |
| US9139692B2 (en) | 2010-12-03 | 2015-09-22 | Basf Se | Process for polymerizing lactam |
| EP2460838A1 (en) | 2010-12-03 | 2012-06-06 | Basf Se | Method for polymerisation of lactam |
| RU2631654C2 (en) | 2013-07-31 | 2017-09-26 | Басф Се | Reversed-phase polymerization method |
| EP3027661A1 (en) | 2013-07-31 | 2016-06-08 | Basf Se | Reverse-phase polymerisation process |
| US10370461B2 (en) * | 2013-07-31 | 2019-08-06 | Basf Se | Reverse-phase polymerization process |
| US9925511B2 (en) * | 2014-06-23 | 2018-03-27 | Basf Se | Apparatus for introduction of droplets of a monomer solution into a reactor |
| CN106573213B (en) * | 2014-06-23 | 2019-11-08 | 巴斯夫欧洲公司 | By device of the droplet distribution of monomer solution into reactor |
| JP2018507310A (en) * | 2015-03-02 | 2018-03-15 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Apparatus for producing powdered poly (meth) acrylate |
| EP3280522B1 (en) * | 2015-04-08 | 2020-08-05 | Basf Se | Apparatus for introduction of droplets into a reactor |
| CN106046341A (en) * | 2016-07-19 | 2016-10-26 | 辽宁科技学院 | Polyoxyfulvene alcohol ether for tackifier and preparation device of polyoxyfulvene alcohol ether |
| CN108970566B (en) * | 2018-08-17 | 2021-03-09 | 北京濮源新材料技术研究院(普通合伙) | Polycondensation reactor with wetting properties for the production of polycarbonate |
| CN110606905A (en) * | 2019-09-16 | 2019-12-24 | 北京泽阳天成化工技术有限公司 | Polypropylene production process and production device |
| CN110813204B (en) * | 2019-11-28 | 2021-09-21 | 齐鲁理工学院 | A biochemical industry reaction vessel for liquid phase contact |
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| NL280053A (en) * | 1961-06-30 | 1900-01-01 | ||
| US3922255A (en) * | 1972-05-15 | 1975-11-25 | Rohm & Haas | Method of producing uniform polymer beads |
| DE3009812C2 (en) * | 1980-03-14 | 1986-06-26 | Peter Dr. 5630 Remscheid Melchior | Process for making beads from polymethacrylate |
| CA1166413A (en) * | 1980-10-30 | 1984-05-01 | Edward E. Timm | Process and apparatus for preparing uniform size polymer beads |
| US4487898A (en) * | 1981-06-12 | 1984-12-11 | Kanegafuchi Chemical Industry Co., Ltd. | Process of continuous suspension polymerization |
| US4623706A (en) * | 1984-08-23 | 1986-11-18 | The Dow Chemical Company | Process for preparing uniformly sized polymer particles by suspension polymerization of vibratorily excited monomers in a gaseous or liquid stream |
| EP0243177B1 (en) * | 1986-04-23 | 1993-07-07 | Sumitomo Chemical Company, Limited | Catalytic production of polyamide block copolymers |
| JP3176607B2 (en) * | 1990-02-07 | 2001-06-18 | 群馬大学長 | Method for forming uniform droplets |
| US5269980A (en) | 1991-08-05 | 1993-12-14 | Northeastern University | Production of polymer particles in powder form using an atomization technique |
| EP0998854B1 (en) * | 1998-02-11 | 2003-05-07 | Transucrania, S.A. | Process and device for producing granulated products |
| WO2002024755A1 (en) * | 2000-09-21 | 2002-03-28 | Merck Patent Gmbh | Polystyrene microspheres and a method for their production |
| JP2008095115A (en) * | 2001-06-22 | 2008-04-24 | Sekisui Chem Co Ltd | Method for producing resin fine particle, resin fine particle and apparatus for producing resin fine particle |
| US6610798B1 (en) * | 2002-10-08 | 2003-08-26 | Nova Chemical Inc. | Controlled suspension polymerization process without mechanical agitation |
| US7727555B2 (en) * | 2005-03-02 | 2010-06-01 | Boston Scientific Scimed, Inc. | Particles |
| DE102005053559A1 (en) * | 2005-11-08 | 2007-05-10 | Basf Ag | Process for the preparation of polymer powders containing vinylformamide units |
| WO2007067145A1 (en) * | 2005-12-07 | 2007-06-14 | Mip Technologies Ab | Monodisperse molecularly imprinted polymer beads |
| JP2008081639A (en) * | 2006-09-28 | 2008-04-10 | Konica Minolta Business Technologies Inc | Toner for developing electrostatic image, resin particle and resin particle polymerization device |
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2010
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2014
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| EP2391668A1 (en) | 2011-12-07 |
| WO2010086433A1 (en) | 2010-08-05 |
| JP2012516901A (en) | 2012-07-26 |
| US20110294968A1 (en) | 2011-12-01 |
| CN102378776A (en) | 2012-03-14 |
| KR20110127173A (en) | 2011-11-24 |
| KR101640272B1 (en) | 2016-07-15 |
| US8883939B2 (en) | 2014-11-11 |
| CN102378776B (en) | 2013-10-30 |
| JP5677979B2 (en) | 2015-02-25 |
| EP2391668B1 (en) | 2017-05-17 |
| US20150038656A1 (en) | 2015-02-05 |
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